Antistatic coating for synthetic fabrics



United States Patent 3,212,927 ANTISTATIC COATING FOR SYNTHETIC FABRICS Earl P. Williams, Pen Argyl, Pa., assignor to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Oct. 1, 1964, Ser.No. 400,919 6 Claims. (Cl. 117138.8)

This application is a continuation-in-part of application Serial No. 270,202, filed on- April 3, 1963, now abandoned.

This invention relates to synthetic fabrics containing fatty acid esters of N-hydroxyalkyl-pynrolidones as antistatic coatings thereon.

I have discovered that N-hydroxyalkyl-pyrrolidone esters of saturated and unsaturated fatty acids of from 6 to 24 carbon atoms are excellent antistatic coatings for synthetic fabrics such as Acrilan, Dacron, nylon, Orion, etc., when employed in an antistatic coating amount varying from 0.5 to 2.5% by weight of the fabric. The fabric may be dyed or undyed.

The esters are characterized by the following general formula:

wherein R and R represent either hydrogen, methyl or ethyl groups, R represents an alkylene radical containing from 1 to 6 carbon atoms and R represents a hydrocarbon residue of a fatty acid of 6 to 24 carbon atoms.

The esters are prepared by esterifying 1 mole of a fatty acid of 6 to 24 carbon atoms with 1 mole of an N-hydroxyalkyl-pyrrolidone by conventional means, preferably in the presence of an acid catalyst such as p-toluene sulfonic acid monohydrate. The N-hydroxyalkyl-pyrrolidones are prepared in the well known manner by reacting at 250 C. 1 mole of an alkanolamine of 1 to 6 carbon atoms with 1 mole of either butyrolactone, S-methyl butyrolactone, 4methyl butyrolactone, 4-ethyl butyrolactone, S-methyl butyrolacto-ne, S-ethyl butyrolactone or 3.3-dimethyl butyrolactone. The alkanolamines utilized in such preparation consist of methanolamine, ethanolamine, 3-amino-propanol-l, 4-amino-butano1-1, S-aminopentano -1 or 6-arnino-hexanol-1.

The fatty acids of 6 to 24 carbon atoms that are esterified with the N-hydroxyalkyl-pynrolidones may be either saturated or unsaturated, aliphatic or aromatic. The nature or character of the acid is immaterial so long as it is capable of esterification with a hydroxyl group. Acids of this type include caproic, capry-llic, capric, lauric, myristic, palmitic, stearic, oleic, linoleic, behenic, tetracosanic, tall oil, hydrogenated tall oil, napthanic or abietic acid, phenoxyalkylcarboxylic, halogenated phenoxylalkylcarboxylic acids, o-p'hthalic acid, alkyl benzoic acids, such as dodecyl-benzoic acid, nonylbenzoic acid, octylbenzoic acid; acids from oxo alcohols and aldehydes, acids from oxidized petroleum fractions; acid mixtures from various natural plant and animal oils such as olive, palm, tallow, castor, peanut, coconut, soybean, cottonseed, ucuhuba, linseed; fish oils such as cod, herring, menhaden, etc.; neatsfoot, sperm, corn, butter, babasse, kapok, hempseed, mustard, nape, safliower, sesame, etc., as well as Emery dimer acids and trimer acids.

3,212,927 Patented Oct. 19, 1965 The esters, prepared as above, are not only effective antistatic coating agents for synthetic fabrics, but are also useful in many diversified applications. For instance, they can be used as wetting, frothing or washing agents in the treatment and refining of textiles; for converting liquid or solid substances, which per se are insoluble in water, into creamy emulsions; for carbonizing; for dyeing; for the pasting of dyestuffs; for fulling; sizing; impregnating and bleaching treatments; as cleansing agents in hard Water; in tanning and mordanting processes; for dyeing acetate with insoluble dyestuffs; for producing foam in fire extinguishers; as a means for improving the absorption power of fibrous bodies; and as an aid in softening baths for hides and skins.

In addition, these esters are valuable emulsifiers for insecticide compositions and agricultural sprays, such as DDT, 2-4-D, toxaphene, chlorodane. These esters are valuable for use as additions to petroleum products, as additives for fuel oils, hydraulic fluids, lubricating oils, cutting oils, greases, as additives to the water or brine used for oil recovery from oil-bearing strata by flooding techniques.

Other valuable uses are in the metal cleaning compositions, dry cleaning compositions, additives for rubber latices, foam inhibitors for synthetic rubber latex emulsions, froth flotation agents, additives for road building materials, as air entraining agents for concrete or cement, additives to asphalt compositions, for incorporation into adhesives, paint, linoleum, for use in bonding agents used in various insulating and building materials, as refining aids in wood digesters to prepare pulp, as additives to pulp slurries in beating operations to prevent foaming and also to aid the beating operation in paper making.

These esters are also useful as emulsifiers for emulsion polymerization, as mercerizing assistants, wetting agents, rewetting agents, dispersing agents, detergents, penetrating agents, softening agents, cutting oils, lime soap dispersants, dishwashing agents, disinfectants, insecticides, herbicides, mothproofing agents, bacteriocides, fungicides and biocides.

They are valuable as antifogging agents for use on glass and other surfaces where the accumulation of an aqueous fog is detrimental. They are useful in the rayon industry as additives to the dope and as aids in clarifying viscose rayon.

These esters are especially useful in breaking petroleum emulsions. They may be used to break emulsions of crude petroleum and salt water as obtained from oil wells by introducing the agent into the well, or to break or prevent emulsions which would result from the water flooding process for recovering oil from oil bearing strata. They may also be used to break emulsions encountered in a petroleum refining process.

They are useful as corrosion inhibitors, as rust inhibitors, in the protection of metals especially ferrous metals, in acid pickling baths, in acid cleaning compositions and in electroplating baths.

Other valuable uses are as solvents, as cleaning agents, for paint brushes, as additives for paints, lacquers, and varnishes, as lubricants, as greases and stufiing agents.

These esters are valuable in the preparation of skin creams, lotions, salves and other cosmetic preparations such as home hairwave sets, shampoos, toothpastes, etc.

The may also be of value in food .products as foaming agents, emulsifying agents, and softening agents.

The following are examples of the preparation of the esters and their application as antistatic agents for synthetic fabrics.

EXAMPLE I In a 500 cc. 4-necked flask equipped with a stirrer, thermometer and downward condenser to receiver EXAMPLE II 63.3 grams (0.4 mole) of pelargonic acid, 51.6 grams (0.4 mole) of N-hydroxyethyl-pyrrolidone and 1.1 grams of p-toluenesulfonic acid monohydrate were heated together at 125160 C./30 mm. for a total of 3% hours during which time a total distillate of 7.3 grams was removed. The final product was neutralized by the addition of 1.0 gram of diethanolamine. Ester No.:199 or 95.3%.

EXAMPLE III In a similar manner 113.7 grams (0.4 mole) of stearic acid, 51.6 grams (0.4 mole) of N-hydroxyethyl-pyrrolidone and 1.6 grams of p-toluenesulfonic acid mono hydrate were heated at l30-l60 C./30 mm. over a period of 2% hours during which time a total of 6.9 grams of distillate were removed. The final product was neutralized by the addition of 1.5 grams of diethanolamine. Ester No.:110.

EXAMPLE IV 84.8 grams (0.4 mole) of double distilled coconut fatty acids, 51.6 grams (0.4 mole) of N-hydroxyethylpyrrolidone and 1.3 grams of p-toluenesulfonic acid monohydrate were reacted together at 120l60 C./ 30 mm. over a period of 5 hours during which time a total of 8.0 grams of distillate were distilled otf. The final product was neutralized by the addition of 1.0 gram of diethanolamine.

EXAMPLE V 68.8 grams (0.4 mole of capric acid, 51.6 grams (0.4 mole) of N-hydroxyethyl-pyrrolidone and 1.2 grams of p-toluenesulfonic acid monohydrate were reacted at 112- 166 C./30 mm. over a period of five hours during which time a total of 7.5 grams of distillate were removed. The final product was neutralized by the addition of 1.2 grams of diethanolamine. Ester No. :201.

' EXAMPLE VI 102.4 grams (0.4 mole) of palmitic acid, 51.6 grams (0.4 mole) of N-hydroxyethyl-pyrrolidone and 1.5 grams of p-toluenesulfonic acid monohydrate were reacted at 110-170 C./ 30 mm. over a period of 4 /2 hours during which time a total of 7.2 grams of distillate were removed. The final product was then neutralized by the addition of 1.2 grams of diethanolamine.

1.7 grams of p-toluenesulfonic acid monohydrate were reacted at 120-155 C./30 mm. over a period of 4 hours during which time a total of 7.2 grams of distillate were removed. The final product was then neutralized by the addition of 1.7 grams of diethanolamine. Ester No.:137.

EXAMPLE VIII Example I was repeated with the exception that 51.6 grams of N-hydroxyethyl-pyrrolidone were replaced by 57.2 grams of N-hydroxypropyl-pyrrolidone. After neutralization with diethanolamine the ester No. was 162 or 93.9%.

EXAMPLE IX Example III was repeated with the exception that 51.6 grams of N-hydroxyethyl-pyrrolidone were replaced by 62.8 grams of N-hydroxybutyl-pyrrolidone. After neutralization with diethanolamine the ester No. was 106 or 80%.

EXAMPLE X Example III was repeated with the exception that 51.6 grams of N-hydroxyethyl-pyrrolidone were replaced by 74.0 grams of N-hydroxyhexyl-pyrrolidone. After neutralization with diethanolamine the product was obtained with an ester No. of 105 or 84.3%.

The method used in determining the antistatic activity of the esters of Examples I to X inclusive is described in the 1957 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists, vol. 33, page 128, titled Antistatic Finish Materials, Determination of the Electrical Resistivity of Fabrics test method 76-1954. In employing this method, the standard procedure is to immerse a ten gram swatch of the synthetic fabric in a 1% solution of the ester antistatic coating agentto 100% pick-up of the solution so that the wetted (coated or sized) fabric weighs twice as much. The wetted (coated) fabric is then dried and conditioned for -the test in the manner described in the Manual.

The esters of Examples I to X were evaluated as follows:

A ten gram swatch each of nylon, Orlon, Dacron and Acrilan fabrics were separately immersed into a (1% aqueous solution of the ester of Example I to obtain a 100% pick-up of the solution of the fabric, i.e., until each of the wetted swatches weighs 20 grams. The wetted (coated) fabrics were dried in an oven at 50 C. and then conditioned for the testing in the testing chamber at a relative humidity of 40% and a temperature of 75 F. for about 25-35 minutes. The same procedure was repeated with the esters of Examples II to X.

. The results of the foregoing test method are shown in Table I.

Table I.'Antistatic activity (log ohms/sq), based on 1 0f antistatic agent by weight of fiber Antistatic Agent of Examples Fiber I II III IV V VI VII VIII IX X Nylon 10. 89 10. 83 10.80 10. 79 10. 69 10.87 10. 80 10. 68 10. 80 10. 88 Orlon- 9. 42 10. 38 10. 40 10. 10. 52 9. 10. 21 10. 57 10. 22 9. Dacrorn 10. 46 I0. 97 10. 90 10. 92 10. 93 10. 44 9. 89 I0. 95 9. 90 10. 56 Acr1lan 10. 20 10. 74 10. 72 10. 80 10. 79 10. 20 9. 79 10. 83 9. 85 10. 30

Average 10. 24 10. 68 10. 10. 74 10. 73 10. 27 10. 17 10. 76 10. 19 10. 34

For controls all of the foregoing fibers were treated with water alone and had resistivities in log ohms/sq.

greater than 14.0 for each fiber.

EXAMPLE VII 118.4 grams (0.2 mole) of Emerys Dimer Acids, 51.6

I claim: 1. Synthetic fibers selected from the class consisting of linear superpolyamides, polyacrylonitrile, and polyethylgrams (0.4 mole) of N-hydroxyethyl-pyrrolidone and ene tetraphthalate having from 0.5% to 2.5% by weight 6 of an antistatic agent as a coating thereon, said agent hav- 5. A synthetic fiber as defined in claim 1 wherein the ing the following general formula: antistatic agent has the formula:

/R R1HC-(I3R 5 R1HO\ /C=O H210 [CH2 H 0 0:0 l (I) 10 (CHM 1:0 R3 (3:0 wherein R and R represent a member selected from the ((13K) BCHS class consisting of hydrogen, methyl and ethyl groups, 15 2 1 R represents an alkylene radical of from 1 to 6 carbon atoms, and R represents a hydrocarbon residue of a fatty acid of from 5 to 23 carbon atoms.

2. A synthetic fiber as defined in claim 1 wherein the A Synthet1 fiber as definad 1n damn I Wherem the antistatic agent has the formula: antstatlc agent has the formula:

Hz(|3CHz H2O C=O .bll' H2? CH2 (CHM 25 H2O\ /C=O f (1 0 (OHM 2)10CHa (l 3. A synthetic fiber as defined in claim 1 wherein the antistatic agent has the formula: ((BHMOHS 112C CH2 1112): I References Cited by the Examiner 5 UNITED STATES PATENTS (5:0 2,718,478 9/55 Fluck etal 117-1395 ((IJHWCH, 2,882,262 4/59 Smith et a1. 260-805 h 2,892,820 6/59 Stewart et a1. 26080.5 4 A synthet1c fiber 3S defined 111 6131111 1 Whfil'fim t e B et 1 antlstatic agent has the formula:

H FOREIGN PATENTS 2C$H2 6 0:0 7,780 11/57 Japan.

OTHER REFERENCES Yakahama et al.: Chemical Abstracts, vol. 52, page 13802d, 1958. E=o WILLIAM D. MARTIN, Primary Examiner. 

1. SYNTHETIC FIBERS SELECTED FROM THE CLASS CONSISTING OF LINEAR SUPERPOLYAMIDES, POLYACRYLONITRILE, AND POLYETHYLENE TETRAPHTHALATE HAVING FROM 0.5% TO 2.5% BY WEIGHT OF AN ANTISTATIC AGENT AS A COATING THEREON, SAID AGENT HAVING THE FOLLOWING GENERAL FORMULA: 